Reversible disulfide cross-linking in layer-by-layer films: preassembly enhanced loading and pH/reductant dually controllable release

This paper describes the fabrication of polyelectrolyte multilayer film which combines preassembly of poly(allylamine hydrochloride) (PAH) and 5,10,15,20-tetraphenyl-21H,23H-porphine-p,p',p' ',p' '-tetrasulfonic acid tetrasodium hydrate (TPPS) in aqueous solution with the layer-by-layer (LbL) assembly of the PAH-TPPS complex and cross-linkable polyelectrolyte, PAASH60, which is a poly(acrylic acid) with 60% of its carboxylic acid grafted of thiol groups. During preassembly, TPPS was incorporated into PAH chains. After oxidative cross-linking to form disulfide bonds in between the layers, the multilayer with preassembly of the PAH-TPPS complex allowed for release and loading of TPPS in a reproducible way. The release of TPPS from the loaded film was a pH-controlled process. To compare with the conventional multilayer, the reloading capacity was greatly enhanced, which was related to the charge binding sites that formed by release of TPPS from the multilayer. Moreover, the release of TPPS could also be achieved by breaking off the cross-linking through reduction of disulfide bonds, and the release rates could be controlled by the reductive efficiency of the reductants in the media. In this way, the release of TPPS is pH/reductant dually controllable, thereby facilitating a new route to multistimuli controllable materials.     

Direct measurements of the interaction between pyrene and graphite in aqueous media by single molecule force spectroscopy: understanding the pi-pi interactions

Pyrene derivatives can absorb onto the surface of carbon nanotubes and graphite particles through pi-pi interactions to functionalize these inorganic building blocks with organic surface moieties. Using single molecule force spectroscopy, we have demonstrated the first direct measurement of the interaction between pyrene and a graphite surface. In particular, we have connected a pyrene molecule onto an AFM tip via a flexible poly(ethylene glycol) (PEG) chain to ensure the formation of a molecular bridge. The pi-pi interaction between pyrene and graphite is thus indicated to be approximately 55 pN with no hysteresis between the desorption and adhesion forces.     

Enhanced Activity and Substrate Specificity by Site-Directed Mutagenesis for the P450 119 Peroxygenase Catalyzed Sulfoxidation of Thioanisole

P450 119 peroxygenase was found to catalyze the sulfoxidation of thioanisole and the sulfonation of sulfoxide in the presence of tert-butyl hydroperoxide (TBHP) for the first time with turnover rates of 1549 min⁻¹ and 196 min⁻¹ respectively. Several mutants were designed to improve the peroxygenation activity and thioanisole specificity by site-directed mutagenesis. The F153G/T213G mutant gave an increase of sulfoxide yield and a decrease of sulfone yield. Moreover the S148P/I161T/K199E/T214V mutant and the K199E mutant with acidic Glu residue contributed to improving the product ratio of sulfoxide to sulfone. Addition of short-alkyl-chain organic acids to the P450 119 peroxygenase-catalyzed sulfur oxidation of thioanisole was investigated. Octanoic acid was found to induce a preferred sulfoxidation of thioanisole catalyzed by the F153G/T213G mutant to give approximately 2.4-fold increase in turnover rate with a k_cat value of 3687 min⁻¹ relative to that of the wild-type, and by the F153G mutant to give the R-sulfoxide up to 30 % ee. The experimental control and the proposed mechanism for the P450 119 peroxygenase-catalyzed sulfoxidation of thioanisole in the presence of octanoic acid suggested that octanoic acid could partially occupy the substrate pocket; meanwhile the F153G mutation could enhance the substrate specificity, which could lead to efficiently regulate the spatial orientation of thioanisole and facilitate the formation of Compound I. This is the most effective catalytic system for the P450 119 peroxygenase-catalyzed sulfoxidation of thioanisole.     

基于裂开型核酸适体非标记荧光法检测ATP

基于裂开型核酸适体序列短、能有效降低因探针形成二级结构产生假阳性信号等优点,选择裂开型核酸适体作为特异性识别探针,核酸染料噻唑橙（TO）为信号探针,用单壁碳纳米管（SWCNTs）降低背景信号,利用“适配体-目标分子-适配体”的“三明治”夹心方式,建立了一种检测ATP的新方法。在pH 8.0的Tris-HCl缓冲溶液中,裂开成两段的ATP适体特异性识别ATP分子,生成稳定的“适配体-ATP-适配体”复合结构。单壁碳纳米管对该复合结构的吸附力较弱,因此该复合物游离在溶液中,TO与其结合而产生强荧光。当不存在ATP时,核酸适体探针以单链状态存在,可通过π-π共轭作用结合到SWCNTs表面,进而不能与TO结合,TO游离在溶液中荧光非常微弱。反应体系中ATP浓度越高,形成的“适配体-ATP-适配体”夹心识别结构复合物越多,检测到的荧光强度越大,据此实现对ATP的检测。在优化实验条件下,在最大荧光发射波长550 nm处,ATP的浓度在9.0×10-9～1.0×10-7 mol·L-1范围内与ΔF/F₀值成线性关系,r=0.996 4。该方法加标回收率为95.2%～104%,相对标准偏差（RSD）为1.02%～4.54%,检出限达到2.67×10-9 mol·L-1。该方法基于功能核酸对目标物亲合力强、选择识别性高的特点,对ATP的检测表现出很好的选择性,实验结果表明,当相对误差控制在±5%以内时,200倍的UTP,GTP和CTP均不干扰ATP的测定。另外,该方法操作简单、快速、无需标记、灵敏准确,可用于血清样品中ATP的测定,在快速检测小分子物质领域中有较好的应用前景。     

缩酮席夫碱类阴离子识别的量子化学研究

缩酮席夫碱是良好的阴离子识别剂,利用量子化学密度泛函理论研究了3种缩酮席夫碱阴离子受体与阴离子客体相结合的空间结构、电荷分布、结合能等方面的变化,计算结果表明,阴离子受体分子的阴离子结合位点位于亚氨基-NH-部,受体分子和阴离子间通过氢键相互作用,阴离子有一部分负电荷转移到受体分子中,且转移的电荷量为R3-3 R3-2 R3-1,在考察的阴离子中,F~-与受体分子的结合能最大,而在3种受体分子中,R3-3对阴离子结合能最大.计算模拟结果,与实验情况相吻合.     

高速杆式弹侵彻下蓄液结构的防护能力

为提高蓄液结构的防护能力,开展蓄液结构弹道侵彻实验,通过改变其前、后面板厚度配比,研究前、后面板不同厚度匹配对蓄液结构破坏模式、压力载荷特性及防护能力的影响。结果表明:弹丸初速是影响入射波压力峰值大小的主要因素。固定前、后面板总厚度不变时,随着前、后面板厚度比的增大,前面板破坏模式由剪切冲塞-薄膜鼓胀-凹陷变形转变为剪切冲塞-薄膜鼓胀直至剪切冲塞破坏,后面板破坏模式由隆起-碟形破坏转变为薄膜鼓胀-花瓣开裂破坏。前、后面板破坏模式是相互影响的,前、后面板厚度匹配关系决定了其相应破坏模式的发生。前面板薄后面板厚的蓄液结构吸收冲击动能更多,抗侵彻能力也更强。     

Multiplicative non-Gaussian noise and additive Gaussian white noise induced transition in a piecewise nonlinear model

We study the transition problems in a piecewise nonlinear model induced by correlated multiplicative non-Gaussian noise and additive Gaussian white noise. Firstly, applying the path integral approach, the unified colored noise approximation, the analytical expression of the steady-state probability density function (SPD) is derived. Then the change regulation of the SPD is analyzed with the change of the strength and relevance of multiplicative noise and additive noise. From numerical computations we obtain some new nonlinear phenomena: the transition can be induced by the cross-correlation strength between noises, the non-Gaussian noise intensity and the Gaussian noise intensity as well as the non-Gaussian noise deviation parameter. This indicates that the effect of the non-Gaussian noise intensity on SPD is the same as that of the Gaussian noise intensity. Moreover, we also find the correlation time of the non-Gaussian noise can not induce the transition.     

丝氨酸异构体的电子-分子形状共振态及其解离动力学理论研究

Shape resonances of electron-molecule system formed in the low-energy electron attachment to four low-lying conformers of serine (serine 1, serine 2, serine 3, and serine 4) in gas phase are investigated using the quantum scattering method with the non-empirical model potentials in single-center expansion. In the attachment energy range of 0-10 eV, three shape resonances for serine 1, serine 2, and serine 4 and four shape resonances for serine 3 are predicted. The one-dimensional potential energy curves of the temporary negative ions of electron-serine are calculated to explore the correlations between the shape resonance and the bond cleavage. The bond-cleavage selectivity of the different resonant states for a certain conformer is demonstrated, and the recent experimental results about the dissociative electron attachment to serine are interpreted on the basis of present calculations.     

Optimization design of chirp managed lasers by integral layer-peeling method

The chirp managed laser (CML) mainly includes a directly modulated laser followed by an optical spectrum reshaper (OSR) filter. In this paper, an integral layer-peeling method has been applied to synthesize the OSR filter with the desired reflection spectrum, which breaks the trade-off between the filter bandwidth and the filter slope steepness inherently existing in the FP etalon based filter, and hence greatly facilitates the optimization design of the OSR for a better transmission performance of a CML. Using this approach, we have, respectively, investigated the optimization design of the OSR filter in terms of the edge slope and the 3 dB bandwidth in the CML modulated at 10 and 25 Gb/s, through studying their transmission performances over the standard single-mode fiber. With the optimum design of OSR, the longest transmission distances at which the power penalty is 1 dB at a bit error rate of 10^?12 are 135 and 18 km for the 10 and 25 Gb/s CML, respectively.     

模态修型减振的旋翼桨毂谐波振动载荷计算

基于模态修型的方法推导了直升机旋翼桨叶根部剪力的计算公式,通过合成桨叶根部载荷推导了旋翼桨毂的谐波振动载荷公式。将本文建立的桨毂谐波载荷计算模型与商用软件CAMRAD计算出的结果进行对比,结果表明:本文所建立模型的旋翼计算频率与CAMRAD计算的频率相比,基阶频率计算误差在2%以内,前十阶频率误差都在8%以内;与已有文献试验测试的桨毂谐波振动载荷相比最大误差在25%以内。说明了本文建立的旋翼桨毂谐波振动载荷计算模型具有可行性和有效性。